In the vibrational strong coupling (VSC) regime, molecular vibrations and resonant low-frequency cavity modes form light-matter hybrid states, vibrational polaritons, with characteristic infrared (IR) spectroscopic signatures. Here, we introduce a molecular quantum chemistry-based computational scheme for linear IR spectra of vibrational polaritons in polyatomic molecules, which perturbatively accounts for nonresonant electron-photon interactions under VSC. Specifically, we formulate a cavity Born-Oppenheimer perturbation theory (CBO-PT) linear response approach, which provides an approximate but systematic description of such electron-photon correlation effects in VSC scenarios while relying on molecular quantum chemistry methods. We identify relevant electron-photon correlation effects at the second order of CBO-PT, which manifest as static polarizability-dependent Hessian corrections and an emerging polarizability-dependent cavity intensity component providing access to transmission spectra commonly measured in vibro-polaritonic chemistry. Illustratively, we address electron-photon correlation effects perturbatively in IR spectra of CO and Fe(CO) vibro-polaritonic models in sound agreement with nonperturbative CBO linear response theory.
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| http://dx.doi.org/10.1021/acs.jpclett.4c00105 | DOI Listing |
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